Polycondensates containing hydroxyquinoline end groups, their use for the preparation of polymers containing metals and metal containing polycondensates

ABSTRACT

The present invention relates to polycondensates of the formula 10, their use for absorbing metal ions of the transition elements of the periodic system and their use for the preparation of polymers containing metals of formula 11 which have e.g. improved resistance to heat and to chemicals compared to the corresponding polycondensates of formula 10.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 549,282 filedFeb. 12, 1975, and now abandoned.

The present invention relates to polycondensates of the formula 10##STR1## wherein R¹ and R² are identical or different and denotehydrogen, (C₁ -C₄)-alkyl, phenyl or halogen (for example chlorine orbromine) and

Z is CH₂, CH--CH₃, an isoalkylidene radical with 3 to 5 carbon atoms, acycloalkylene or cycloalkylidene radical with 5 to 15 carbon atoms, or aradical of the formulae 2 ##STR2## in which R⁴,R⁵ and R³ are identicalor different alkyl radicals with 1 to 5 carbon atoms, and M is apolycarbonate segment, preferably of the formula ##STR3## or a polyestersegment, preferably of the formula ##STR4## or a polyamide segment,preferably of the formula ##STR5##

The polycarbonate segments have molecular weights Mn in the range from1,000 to 30,000; the polyester segments and the polyamide segments havemolecular weights Mn in the range from 800 to 25,000. (Mn is determinedby membrane osmometry in usual solvents at 20° C.).

In the polycarbonate segments M₁

D is chlorine, bromine, hydrogen or C₁ -C₄ -alkyl,

L is a single bond, C₁ -C₅ -alkylene, C₂ -C₅ -alkylidene,

C₅ -C₁₅ -cycloalkylene, C₅ -C₁₅ -cycloalkylidene or a radical of thefollowing formula ##STR6## p is an integer between 2 and 50; in thepolyester segments M₂

R and R' are identical or different and denote C₂ -C₁₂ -alkylene whichcan be interrupted by --O-- or cyclohexylene, C₅ -C₁₅ -cycloalkylene, C₈-C₁₂ -arylenedialkylene, for example C₈ -C₁₂ -phenylenedialkylene,

C₆ -C₁₂ -arylene, for example phenylene, naphthylene or diphenylene, andC₁₃ -C₁₅ -alkylidene-diphenylene and

p denotes an integer between 2 and 50;

in the polyamide segments M₃

R" is hydrogen and C₁ -C₄ -alkyl, and

R, R' and p are as defined in M₂.

A process for the preparation of the polycondensates according to theinvention, containing 8-hydroxyquinoline end groups, of the formula 10is to co-condense 8-hydroxyquinolines of the formula 1 ##STR7## in whichX represents OH or NH₂ or NH--(C₁ -C₄)-alkyl,

R¹ and R² are identical or different and denote hydrogen, (C₁-C₄)-alkyl, phenyl or halogen (for example chlorine or bromine) and

Z denotes CH₂, CH--CH₃, an isoalkylidene radical with 3 to 5 carbonatoms, a cycloalkylene or cycloalkylidene radical with 5 to 15 carbonatoms or a radical of the formulae 2 ##STR8## and which are described inGerman Patent Application P 24 07 308 (Le A 15 355) filed on the sameday, directly with the starting compounds which are needed to synthesisethe polycondensate segments M of the formula 10 in accordance with knownprocesses.

In carrying out this process it was found, surprisingly, that, forexample, when preparing polycarbonates with 8-hydroxyquinoline endgroups in accordance with the processes customary for polycarbonatesyntheses, the functional 8-hydroxyquinolines of the formula 1 (X═OH)added in the condensation reaction are condensed onto the chain end andthus react specifically as chain stoppers, so that the complex-formingcentre of the 8-hydroxyquinolyl radical remains preserved.

The action of the functional 8-hydroxyquinolines as chain stoppers wasconfirmed by means of end group analysis and by comparison of themolecular weights determined in this way with the measured values fromindependent molecular weight determinations (e.g. determination viaviscosity or membrane osmometry).

By controlled addition of the functional 8-hydroxyquinolines of theformula 1, in amounts of 2 mol % to 50 mol % relative to the sum of theremaining starting compounds, as chain stoppers, it is possible toobtain polycondensates, with 8-hydroxyquinoline end groups of theformula 10, of the desired chain length, in which the polymer units p ofthe polycarbonates, polyesters or polyamides, as defined above forformula 10, can be present two-fold to fifty-fold.

Compounds of the formula 10 are prepared, depending on the nature of thedesired polycondensate segments, in accordance with the variantscustomary for the preparation of polycondensates, the radical X of thefunctional hydroxyquinolines of the formula I being OH for the synthesisof polycarbonates and polyesters and NH₂ or NH--(C₁ -C₄ -alkyl) for thesynthesis of polyamides.

A preferred process for the preparation of the polycarbonates with8-hydroxyquinoline end groups according to the formula 10 (M=M₁) is, forexample, the react bis-phenol components, together with the functional8-hydroxyquinolines of the formula 1 (X═OH), under the conditions of aphase boundary reaction, with phosgene or with the bis-chlorocarbonicacid esters of bis-phenol components in a mixture of an aproticwater-immiscible solvent, such as, for example, dichloroethane,methylene chloride, chloroform, monochlorobenzene and dichlorobenzene,and aqueous alkali metal hydroxide solution, in the presence of suitablecatalysts, for example triethylamine. At temperatures around 20° C. thatis between 0° C. and 40° C., somewhat more than the equimolar amount ofphosgene is employed for this reaction.

To control the molecular weight, up to 50 mol %, based on the sum of theremaining starting substances, of the functional 8-hydroxyquinolines ofthe formula 1 (X═OH) are used as chain stoppers.

The polycarbonates can be worked up in accordance with customaryprocesses such as, for example, by precipitation or by evaporation ofthe solvent, in which case the phase containing the polycarbonate ispreferably first washed until free of electrolyte. (Literature on thepreparation of polycarbonates: H. Schnell, Chemistry and Physics ofPolycarbonates, Interscience Publishers, London 1964).

Examples of suitable diphenols for the preparation of polycarbonatesaccording to the formula 10 (M═M₁) are 4,4'-dihydroxydiphenyl,bis-(4-hydroxyphenyl)-propane-2,2 (bisphenol A),bis-(4-hydroxy-3,5-dichloro-phenyl)-propane-2,2 (tetrachlorobisphenol),bis-(4-hydroxy-3,5-dibromophenyl)-propane-2,2 (tetrabromobisphenol A),bis-(4-hydroxy-b 3,5-dimethylphenyl)-propane-2,2 (tetramethylbisphenolA), bis-(4-hydroxy-3-methyl-phenyl)-propane-2,2 andbis-(4-hydroxyphenyl)-cyclohexane-1,1 (bisphenol Z). Further diphenolssuitable for the preparation of polycarbonates are described in U.S.Pat. Nos. 3,028,365, 2,999,835, 3,148,172, 3,271,368, 2,970,131,2,991,273, 3,271,367, 3,280,078, 3,014,891 and 2,999,846 and in GermanOffenlegungsschriften (German Published Specifications) No. 2,063,050(Le A 13 359), No. 2,063,052 (Le A 13 425), No. 2,211,957 (Le A 14 240)and 2,211,956 (Le A 14 249).

Several processes are available for the preparation of polyesters with8-hydroxyquinoline end groups according to the formula 10 (M═M₂). Acustomary process which is preferentially suitable for the preparationof the polyesters from glycols and aromatic dicarboxylic acid esters isthe trans-esterification process. In this process, as is known, thedicarboxylic acid esters of readily volatile alcohols, such as, forexample, terephthalic acid dimethyl ester, are condensed withappropriate glycols, such as, for example, ethylene glycol, attemperatures of 120°-300° C., optionally using reduced pressure andoptionally in the presence of acid or basic catalysts, for examplemineral acids or alkali metal alcoholates and alkaline earth metalalcoholates, and with the functional 8-hydroxyquinolines of the formula1 (X═OH), and the dicarboxylic acid esters can be added in an excess ofup to 50 mol %, relative to the glycol component, depending on thedesired degree of polymerisation of the polyester.

(Literature on the trans-esterification process: W. H. Carothers and F.J. van Natta, J. Amer. Chem. Soc. 52, 314 (1930); U.S. Pat. No.2,534,028 (1948), Du Pont, inventor: E. F. Izard).

If polyesters of the formula 10 (M═M₂) based on diphenols and aromaticdicarboxylic acids are desired, it is possible to use the process ofsolution polycondensation with dicarboxylic acid chlorides, for exampleisophthalic acid dichloride, and bisphenols, for example bisphenol A, asstarting compounds, with the reaction with the functional8-hydroxyquinolines of the formula 1 (X═OH) preferably being carried outby the variant of phase boundary condensation at about 20° C. and thesum of the phenolic components being employed in a slight excessrelatively to the bifunctional acid chloride. At times it may beadvisable to add a wetting agent such as, for example, sodiumlauryl-sulphate. Suitable solvents are CH₂ Cl₂, CHCl₃, dichloroethane,monochlorobenzene and dichlorobenzene. In this method, it is anadvantage that the reactivity of the functional groups of the8-hydroxyquinolines according to the formula 1 (X═OH) differs and almostquantitatively only the functional centre X participates in thecondensation. (Literature on solution polycondensation: H. Batzer, H.Holtschmidt, F. W. Wiloth and B. Mohr, Makromolekulare Chemie 7, 82(1951); W. R. Sorenson and T. W. Campbell: Praparative Methoden derPolymeren-Chemie (Preparative Methods in Polymer Chemistry), page 118,Verlag Chemie, Weinheim 1962).

The polyesters of the formula 10 (M═M₂) based on aliphatic orcycloaliphatic carboxylic acids and glycols or aliphatic orcycloaliphatic carboxylic acids and diphenols are also obtainedaccording to one of the processes mentioned.

Examples of suitable dicarboxylic acids, or of their esters, anhydridesand chlorides, for the preparation of polyesters according to theformula 10 (M═M₂) are terephthalic acid, isophthalic acid, phthalicacid, methylterephthalic acid, naphthalenedicarboxylic acid,diphenyldicarboxylic acid, diphenylmethanedicarboxylic acid, adipicacid, succinic acid, glutaric acid, sebacic acid, pimelic acid, subericacid, azelaic acid, diglycollic acid, cyclohexanedicarboxylic acid andcyclohexanediacetic acid. The preferred lower aliphatic esters of suchacids are dimethyl esters, diethyl esters and dipropyl esters andmixtures of these.

Examples of glycols which can be used are: ethylene glycol, diethyleneglycol and triethylene glycol, 1,2-propanediol and 1,3-propanediol,1,4-, 2,3- and 1,3-butanediol, 1,6-hexanediol, 1,10-decanediol,cyclohexanedimethanol, cyclohexanediol, 2,2-dimethyl-propanediol-(1,3),glycerine monomethyl ether and mixtures of the dihydric alcohols.

Suitable diphenols which can be used are those already mentioned inconnection with the synthesis of the polycarbonates.

Several processes are available for the preparation of polyamides with8-hydroxyquinoline end groups according to the formula 10 (M═M₃), basedon preferably aliphatic diamines and aliphatic or aromatic dicarboxylicacids as well as the 8-hydroxyquinolines of the formula 1 (X═NH₂ orNH--(C₁ -C₄)--alkyl).

A customary process is the reaction of bifunctional acid chlorides, suchas, for example, sebacyl chloride, with suitable diamines, such as, forexample, hexamethylenediamine and the appropriate functional8-hydroxyquinolines of the formula 1 (X═NH₂ or NH--(C₁ -C₄)--alkyl),wherein the bis-acyl chloride, in a water-immiscible organic solvent,for example tetrachloroethylene, is reacted with the aqueous solution ofthe diamine and of the hydroxyquinoline of the formula 1 which is to beused, in a phase boundary condensation. This process makes it possibleto use in particular those reactants where a thermal polycondensationpresents difficulties. The reaction is run at temperatures around 20° C.and below, and in general the sum of the two amine components can beadded in a slight excess relative to the bifunctional acid chloride.

(Literature: E. L. Wittbecker and P. Morgan, J. Polymer Sci. 40, 289(1959) and P. W. Morgan and S. L. Kwolek, J. chem. Educ. 36, 182, 530(1959)).

A further process permits the direct polycondensation of diamine,dicarboxylic acids and the functional 8-hydroxyquinolines of the formula1 (X═NH₂ or NH--(C₁ -C₄ -alkyl), in which case the water produced in thereaction must be removed continuously from the reaction space, forexample by vacuum, since it is a reaction parameter having a substantialinfluence on the rate of polyamide formation. This process is carriedout in bulk or in an inert diluent, for example xylenol, at temperaturesof 180°-250° C.

Since the reaction in the first place produces a salt, it is alsopossible to employ directly the salt obtained beforehand from thecorresponding diamines and dicarboxylic acids. (Literature: DRP 749,747(1935), Du Point; Laboratory Instructions by W. Lehmann, Bayer AG, seeHouben-Weyl, Methoden der Org. Chemie (Methods of Organic Chemistry),volume XIV, 2, page 136 (1963), Thieme Verlag, Stuttgart).

Suitable dicarboxylic acids and their derivatives are the bifunctionalacids already mentioned in connection with the preparation of thepolyesters with 8-hydroxyquinoline end groups. The following diaminesare examples of suitable amine components: ethylenediamine,trimethylenediamine, tetramethylenediamine, pentamethylenediamine,hexamethylenediamine, decamethylenediamine,4,4'-diamino-dicyclohexylmethane and m- and p-phenylenediamine, anddiphenyldiamine.

The diamines and dicarboxylic acids can of course also optionally beco-condensed with suitable aminocarboxylic acids such as, for example,6-amino-caproic acid, 11-amino-undecanoic acid or their lactams, in theform of a melt condensation with exclusion of oxygen (literature: M. R.Aelion, Annales de Chemie (12) 3, 5 (1948)).

A further subject of the present specification is thus a process for thepreparation of the compounds of the formula 10, which is characterisedin that for the preparation of the polycondensates of the structuralpart M in accordance with known processes, 8-hydroxyquinolines of theformula 1 are used as reactants.

The polycondensates according to the invention, carrying8-hydroxyquinoline end groups, in accordance with the formula 10, can beemployed, in a suitable form, for removing metal ions of the transitionelements of the periodic system, that is to say the elements Sc to Zn(atomic numbers 21 to 30), Y to Cd (atomic numbers 39-48), La to Hg(atomic numbers 57-80), Ac to U (atomic numbers 89-92) and also Mg, Ca,Al, Pb and Bi from solutions or industrial effluents. The absorption ofthe metal ions is reversible; thus they can easily again be separatedfrom the polycarbonate by washing, for example with acids orcomplex-forming agents.

The polycondensates according to the invention can also be employed forcomplexing interfering metallic impurities in thermoplastics orthermosetting resins in amounts of 0.01% by weight to 10% by weight,based on the total mixture.

The polycondensates according to the invention, of the formula 10, canalso be used for the preparation of polymers containing metal.

The subject of the present specification thus also embraces a processfor the preparation of polymers containing metal, of the followingformula 11 ##STR9## wherein Q is either a group of the formula 10 a or Tand ##STR10## wherein R¹, R², Z and M are defined in accordance with theformula 10,

n is between 1 and 50 and

G corresponds to the metal compounds of the formula 12 a ##STR11## inwhich m is the number of anion bonds and/or ligands T on the metal atomand is calculated from the difference of the valency or co-ordinationnumber minus two, r is an integer from 0 to 20,

Me is a metal of sub-group 1 to 8 or of main group 2 to 5, especiallyone of the elements Sc to Zn (atomic numbers 21 to 30), Y to Cd (atomicnumbers 39 to 48),

La to Hg (atomic numbers 57 to 80), Ac to U (atomic numbers 89 to 92),Al, Pb and Bi, and

T corresponds to anions of inorganic mineral acids, anions of organiccarboxylic acids, complex-forming agents, C₁ -C₁₈ -alkoxy radicals, C₆-C₁₂ -aryloxy radicals and/or trialkylsiloxy radicals with 3 to 12C-atoms and E is H or ##STR12## which is characterised in that thepolycondensates of the formula 10 are reacted with metal compounds ofthe formula 12 ##STR13## (a) in homogeneous solution in aprotic solventsat temperatures between 20° C. and 160° C., using molar ratios of thecompounds 10:12 which are between 1:0,5 and 1:1 and using concentrationsof 10 and 12 in solution which are between 0.001% by weight and 30% byweight, or

(b) if T only corresponds to anions of inorganic mineral acids, anionsof organic carboxylic acids and/or complex-forming agents, by two-phasereaction of the compounds of the formula 10 in aprotic solvents and ofthe compounds of the formula 12 in polar protic solvents at temperaturesbetween 20° C. and 220° C., in a molar ratio of the compounds 10:12 ofbetween 1:0,5 and 1:1 and in concentrations of 1-30% by weight of thepolycondensates of the formula 10 and of 0.001-30% by weight of themetal compounds of the formula 12. Inorganic mineral acids useful forpreparing anions T are especially HCl, H₂ SO₄, H₃ PO₄ and HNO₃ ; organiccarboxylic acids useful for preparing anions T are especially saturatedaliphatic C₁ -C₁₈ carboxylic acids (e.g. HCOOH, (COOH)₂, CH₃ -COOH andCH₃ --(CH₂)₁₆ --COOH); as complex forming agents are suitable especiallyaliphatic diketones (e.g. acetylacetone) ethylendiamintetraacetic acid,nitrilotriacetic acid and cyclopentadiene.

The subject of the present specification thus also embraces polymers 11containing metal, prepared using the polycondensates of the formula 10in accordance with the abovementioned processes.

In the polymers according to the invention, containing metal, of theformula 11, obtained by reaction of polycondensates of the formula 10with metal compounds of the formula 12, the polycondensates, containing8-hydroxyquinoline end groups, are linked via the metals or metal oxidesin general by linear chain formation, with stable inner complexes of the8-hydroxyquinoline radicals with the metals being formed. (Compare R.Berg "Die analytische Verwendung von o-Oxychinolin ("Oxin") und seinerDerivate" ("The Analytical Use of o-Hydroxyquinoline ("Oxine") and ofits Derivatives"), 2nd edition, Stuttgart 1938, and R. Bock, Angew.Chemie 67, 420 (1955)).

A partial branching or crosslinking of the linear polymers, containingmetal, of the formula 11 can however be achieved subsequently byreaction of the ligands T still present on the metal compounds of theformula 12a.

Thus, for example, when using titanium tetrabutylate as the metalcompound for linking polycondensates of the formula 10, the butoxyradicals remaining on the titanium after the chain lengthening reactioncan be split off on addition of water and the titanium atoms ofdifferent polymer chains bonded to one another by oxygen bridges.

The linear chain lengthening can be observed from the rise in therelative viscosity and from determination of the numerical average Mnfrom osmometric measurements.

The desired chain length can be obtained by varying the molar ratio ofmetal compound to polycondensate of the formula 10.

With a molar ratio of polycondensate 10 to metal compound of 1:1 linearpolymers 11 are obtained, with a molar ratio of polycondensate 10 tometal compound of 1:0,5 dimeric products of formula 11 are obtained.

Equally, the metal content of the polymers of the formula 11 can bevaried in accordance with the amount of metal compound employed and canbe up to 30% by weight, referred to the polymer 11 in question.

Examples of suitable metal compounds for the preparation of thepolymers, containing metal, of the formula 11, are the followingcompounds of the metals of the 1st to 8th sub-group and of the 2nd to5th main group:

(a) Inorganic salts and their aquo-complexes, such as, for example,FeCl₃, FeCl₃ ×6 H₂ O, CuSO₄, CuSO₄ ×5 H₂ O, CrCl₃ ×6 H₂ O, CoCl₂, MnSO₄×7 H₂ O, NiSO₄ ×6 H₂ O, AlCl₃ ×6 H₂ O;

(b) Salts of organic acids, such as, for example, Cu(C₂ H₃ O₂)₂, Ni(C₂H₃ O₂)₂, Co(C₂ H₃ O₂)₂, Zn(C₂ H₃ O₂)₂, Cu(C₇ H₅ O₂)₂, AgC₇ H₅ O₂, ZnC₂O₄, CrC₂ O₄, CoC₂ O₄ ×2 H₂ O

(c) Alcoholates and phenolates, such as, for example, Zr(C₄ H₉ O)₄,Ti(C₄ H₉ O)₄, Zr(C₁₈ H₃₇ O)₄, Ti(C₁₈ H₃₇ C₄)₄, Ti(CH₃ C₆ H₄ O)₄, B(C₂ H₅O)₃, B(C₄ H₉ O)₃

(d) Metal complexes, such as, for example, the acetylacetonates Co(C₅ H₇O₂)₂, Ni(C₅ H₇ O₂)₂, Fe(C₅ H₇ O₂)₃, Mn(C₅ H₇ O₂)₂, Zr(C₅ H₇ O₂)₄ andbis-(cyclopentadienyl)-titanium dichloride.

(e) Aggregated metal compounds such as, for example, n-butyltitanatepolymer, cresyl-titanate polymer and (trimethylsiloxy)-titanate polymer.

In these, the degree of polymerisation can be between 1 and 20. (See thecorresponding company publication by Dynamit Nobel).

The reaction of the abovementioned metal compounds with thepolycondensates of the formula 10 can be carried out in homogeneoussolution or as a phase boundary reaction.

The reaction in homogeneous solution is carried out in aprotic solventssuch as, for example, acetone, acetonitrile, nitromethane, benzene,toluene, xylene, monochlorobenzene and dichlorobenzene,dimethylformamide and dimethylacetamide, dichloroethane, methylenechloride, chloroform, diethers of ethylene glycol and the like. Thestarting compounds can be brought together direct, preferably in theform of solutions of defined composition, of which the concentrationrange is from 0.001 to 30% by weight of starting compound in solution,using ratios of equivalent solved reactants of8-hydroxyquinoline/polycondensate and metal compound of between 1:0,5and 1:1, at temperatures between 20° C. and 160° C., it being moreadvantageous to add the metal compounds to the polycondensates,containing 8-hydroxyquinoline end groups, of the formula 10.

In the phase boundary reaction, the polycondensates of the formula 10are dissolved in aprotic and water-immisicible solvents such as, forexample, benzene, toluene, xylene, monochlorobenzene and dichlorobenzeneand chlorinated hydrocarbons such as, for example, dichloroethane,methylene chloride, chloroform and the like. The metal compounds of theformula 12, in which T can only represent anions of inorganic mineralacids, anions of organic carboxylic acids and/or complex-forming agents,are employed as a solution in a protic solvent, preferably water. In thephase boundary reaction, it is possible to use a greater excess of metalcompound of the formula 12, since unreacted metal compound remains inthe protic solvent. The reactions are carried out at temperaturesbetween 20° and 220° C. and in concentrations of 1-30% by weight asregards the polycondensates of the formula 10 and between 0.001 and 30%by weight as regards the metal compounds of the formula 12.

The metal-containing polymers of formula 11 have because of their metalcontent an increased resistance to heat (measured according DIN 53 735),an increase resistance to chemicals (measured according DIN 53 476), ahigher glass transition temperature and a reduced stress cracking(measured according DIN 53 449) compared to the corresponding metal-freepolycondensates with 8-hydroxyquinoline end groups of formula 10.

Both types of polycondensate compounds, the metal-free of formula 10 andthe metal-containing of formula 11 are according the polymer segments Mof technical and commercial use: Thus the polycondensates of formulae 10and 11 based on M₁ according the corresponding polycarbonates with theend groups known in the art (e.g. p-tert.-butylphenyl-end groups)instead of those derived from the 8-hydroxychinolines of formula 1according the instant invention; the polyesters of formulae 10 and 11based on M₂ according the corresponding polyesters with the end groupsknown in the art instead of those derived from the 8-hydroxychinolinesof formula 1 according the instant invention; the polyamides of formulae10 and 11 based on M₃ according the corresponding polyamides with theend groups known in the art instead of those derived from the8-hydroxychinolines of formula 1 according the instant invention.

From the use of the 8-hydroxychinolines of formula 1 as end groups forthe polycondensates of the types M₁, M₂ and M₃ of formula 10 thereresult the additional, already mentioned (page 11) complexing propertiesof these polycondensates; from the reaction of the compounds of formula10 to the metal-containing of formula 11 according to instantspecification there result the improved properties mentioned above.

Hence, the subject of the present patent application also includes newpolymers, containing metal, of the formula 11 ##STR14## wherein Q iseither a group of the formula 10 a or T, and wherein R¹, R², Z and M aredefined in accordance with formula 10,

n is between 1 and 50 and

G corresponds to the metal compounds of the formula 12a ##STR15## inwhich m is the number of anion bonds and/or ligands T on the metal atomand is calculated from the difference of the valency or co-ordinationnumber minus two,

r is an integer from 0 to 20,

Me is a metal of sub-group 1 to 8 or of main group 2 to 5, especiallyone of the elements Sc to Zn (atomic numbers 21 to 30), Y to Cd (atomicnumbers 39 to 48), La to Hg (atomic numbers 57 to 80), Ac to U (atomicnumbers 89 to 92), Al, Pb and Bi, and

T corresponds to anions of inorganic mineral acids, anions of organiccarboxylic acids, complex-forming agents, C₁ -C₁₈ -alkoxy radicals, C₆-C₁₂ -aryloxy radicals and/or trialkylsiloxy radicals with 3 to 12C-atoms and

E is H or ##STR16##

The polymers according to the invention, containing metal, of theformula 11, can be used, by themselves or as a constituent of a polymerblend, for the production of weathering-resistant, corrosion-resistant,solvent-resistant and heat-resistant coatings, as sizing agents and asadhesion promoters between metals, metal oxides, glass surfaces andsubsequently applied plastics and lacquers. The metal-containingpolymers 11 are suitable products for all those purposes, where usuallythe corresponding polycarbonates, polyesters or polyamides are used.

The polymers according to the invention, containing metal, of theformula 11, can be used as stabilisers for plastics. Such plastics arepolyvinyl chloride or its copolymers such as ethylene/vinyl chloridecopolymer or vinyl acetate/vinyl chloride copolymer, polyethylene,polypropylene, polyacrylates, copolymers of acrylates or methacrylatesand at least one further monomer, vinyl acetate polymers, ethylene/vinylacetate copolymers, polycarbonates, polysulphones, polyphenylene oxides,styrene copolymers, polymers of the ABS type(acrylonitrile-butadiene-styrene graft polymer thermoplastics),polyamides of the nylon type or polycaprolactam, polyethyleneterephthalates, polyacetals and the like.

In addition, the polymers containing metal, of the formula 11, can beused as catalysts and, for example in the form of the cobalt compounds,as initiators for reactions which take place by a radical mechanism.

The following description of the starting compounds for thepolycondensates 10, namely the new functional 8-hydroxyquinolines of theformula 1 ##STR17## in which X represents OH or NH₂ or NH--(C₁--C₄)-alkyl,

R¹ and R² are identical or different and denote hydrogen, (C₁-C₄)-alkyl, phenyl or halogen (for example, chlorine or bromine) and

Z is CH₂, CH--CH₃, an isoalkylidene radical with 3 to 5 carbon atoms, acycloalkylene or cycloalkylidene radical with 5 to 15 carbon atoms, or aradical of the formulae 2 ##STR18## in which R⁴, R⁵ and R³ are identicalor different alkyl radicals with 1 to 5 carbon atoms,

is taken mainly from the German Patent Application No. P 24 07 308 (Le A15 355).

As isoalkylidene radicals Z of formula 1 there are to be understood theradicals ##STR19##

Suitable process for the preparation of the functional8-hydroxyquinolines of formula 1 are the reaction of 8-hydroxyquinolinewith (cyclo)alkenyl-substituted phenols or (cyclo)alkenyl-substitutedanilines or with compounds which are also able to form carbonium ionsunder the influence of acid catalysts, say halogenoalkyl-substitutedphenols or anilines or hydroxyalkyl-substituted phenols or anilines,according to the methods, which are in themselves known, for thealkylation of hydroxyaryl compounds, in which methodsit is also possiblefor the components suitable for the alkylation of 8-hydroxyquinoline,for example the hydroxyalkyl-substituted phenols, only to be produced insitu, for example from corresponding phenols and correspondingaldehydes, during the alkylation of 8-hydroxyquinoline.

The compounds of the formula 1 in which Z═CH₂ are obtained by reactionof 8-hydroxyquinoline with compounds of the formula 3 ##STR20## in whichX, R¹ and R² have the same meaning as in the formula 1 and in which

Y represents the hydroxymethyl or halogenomethyl radical

the molar ratio of the reactants (8-hydroxyquinoline to compounds of theformula 3) preferably being between 1:1 and 10:1.

In the case of compounds of the formula 3 in which Y is halogenomethyl,preferably chloromethyl and bromomethyl, it is only possible to useLewis acids such as, for example, aluminium-(III) chloride or borontrifluoride, as the catalysts, in amounts between 10 mol % and 100 mol%, relative to compounds of the formula 3.

Preferably, compounds of the formula 3, with Y being hydroxymethyl, areemployed; these are easily obtainable from formaldehyde and thecorresponding phenols and anilines. Alkylation catalysts used for thispurpose are Lewis acids, hydrosilicates of the montmorillonite type andmineral acids and carboxylic acids which can, as for example in the caseof acetic acid, also be used directly as solvents, in amounts between 10mol % and 500 mol %, relative to compounds of the formula 3.

Depending on the nature of the starting substances and of the catalyst,the reaction can be carried out in bulk or in solution and in atemperature range of 10°-150° C., the choice of the solvent depending onthe solubility of the starting materials, the reaction temperature and,especially, the catalyst.

Only those solvents can be selected which are not alkylated under theparticular reaction conditions and which themselves do not have analkylating action, such as, for example, carbon disulphide,nitromethane, nitrobenzene, and, if appropriate, carboxylic acids, suchas, for example, formic acid or acetic acid, and, in the absence ofLewis acids as catalysts, chlorinated aliphatic hydrocarbons, forexample methylene chloride or dichloroethane, if appropriate.(Literature: Houben-Weyl, Methoden der organischen Chemie (Methods ofOrganic Chemistry), volume V/la, page 509, Thieme Verlag, Stuttgart1970).

The compounds of the formula 1, in which

Z is CH--CH₃, an isoalkylidene radical with 3 to 5 carbon atoms, acycloalkylidene radical with 5-15

C atoms or a radical of the formulae 2 are obtained by reaction of8-hydroxyquinoline with compounds of the formula 3 ##STR21## in which X,R¹ and R² have the same meaning as in the formula 1 and in which

Y is vinyl, an alken-(1)-yl-(2) radical with 3 to 5 C atoms, analken-(2)-yl-(2) radical with 4 to 5 C atoms, an alken--(2)--yl--(3)radical with 5 C atoms, a cycloalken---(1)--yl--(1) radical with 5 to 15C atoms or a radical of the formulae 4 ##STR22## wherein R³, R⁴, R⁵ andR⁷ are identical or different and denote alkyl radicals with 1-5 C atomsand

R⁶ is H or a C₁ -C₄ -alkyl radical.

The alkenyl or cycloalkenyl radicals in the compounds of the formula 3can also be present masked as HCl adducts or H₂ O adducts. When usingthe H₂ O adducts, it is preferred to employ proton acids, such as, forexample, hydrofluoric acid or sulphuric acid, as the catalyst, in whichcase the alkylation is preceded by the dehydration of the alcohol to theolefine. Lewis acids can also be used as catalysts (literature: A.Schriesheim in G. A. Olah, Friedel Crafts and Related Reactions, vol.II, page 477, Interscience Publishers, New York, London, Sidney 1964).The alkylation by means of the corresponding halides is also catalysedby Lewis acids. To avoid excessive isomer formation, the alkylation viathe alcohols and halides is carried out at temperatures as low aspossible in the range from 10° to 150° C., in bulk or in solution, usingthe solvents which have already been mentioned above.

The preferentially used alkylation of 8-hydroxyquinoline with the(cyclo)alkenyl compounds of the formula 3 is carried out in bulk or insolution, at temperatures between 50° and 250° C., preferably between100° and 200° C., using acid catalysis with Lewis acids, hydrosilicatesand proton acids. The catalyst is added in amounts of 10 to 200 mol %,depending on the starting substances, and the molar ratio of thereactants, olefinic alkylating agent to 8-hydroxyquinoline, is generallypreferentially between 1:1 and 1:10, but can also lie outside thisrange. Suitable catalysts to be used are Lewis acids such as, forexample, aluminium-(III) chloride, iron-(III) chloride, tin chloride,titanium tetrachloride, boron trifluoride and mixed catalysts of thetype of AlCl₂.HSO₄ or AlBr₂.H₂ PO₄, or proton acids such as, forexample, hydrogen chloride, hydrofluoric acid, concentrated phosphoricacid, sulphuric acid from a concentration of 96% upwards, oxalic acidand toluenesulphonic acid. Acid activated aluminas such as bentonites,zeolites and other hydrosilicates, and ion exchange resins such as, forexample, those based on polystyrenes carrying sulphonic acid groups, orphenolic resins, carrying sulphonic acid groups, which are insoluble inthe reaction mixture, are also advantageous. The alkylation of8-hydroxyquinoline with the (cyclo)alkenyl compounds can be carried outin bulk and in solution.

Examples of suitable solvents are nitrobenzene, nitromethane and carbondisulphide.

(Literature on the catalysis: V. N. Ipatieff and L. Schmerling, inAdvances in Catalysis, volume 1, pages 27-64, Academic Press Inc.Publishers, New York 1950; literature on the alkylation with olefines:G. A. Olah, Friedel Crafts and Related Reactions, Vol. I, IntersciencePublishers, New York, London, Sidney, 1963; F. Asinger et al. Erdol,Kohle 20, 786, 852 (1967)).

The compounds of the formula 1, in which Z is a cycloalkylene radicalwith 5 to 15 C atoms, are obtainable by reaction of 8-hydroxyquinolinewith compounds of the formula 3, in which Y is a correspondinghydroxy-cycloalkyl radical with 5-15 C atoms, though isomerisations atthe cycloalkyl radical cannot be avoided entirely.

The subject of P 24 07 308 (Le A 15 355) thus also embraces a processfor the preparation of the compounds of the formula 1; this ischaracterised in that 8-hydroxyquinoline is alkylated with compounds ofthe formula 3 in which

X, R¹ and R² have the same meaning as in the formula 1 and

Y is hydroxymethyl or halogenomethyl, vinyl, an alken--(1)--yl--(2)radical with 3-5 C atoms, an alken-(2)--yl--(2) radical with 4 to 5 Catoms, an alken-(2)-yl-(3) radical with 5 C atoms, acycloalken-(1)-yl-(1) radical with 5 to 15 C atoms or a radical of theformulae 4, or a hydroxycycloalkyl radical with 5-15 C atoms

in the presence of acid catalysts, in accordance with the known methodsfor the alkylation of hydroxyaryl compounds, with the molar ratio of thereactants 8-hydroxyquinoline and a compound of formula 3 being between1:1 to 10:1.

Instead of the (cyclo)alkenyl-substituted phenols or anilines of theformula 3 it is also possible to employ corresponding compounds whichare also capable of forming, under the influence of acid catalysts,carbonium ions of the formula 1a ##STR23## wherein X, R¹, R² and Z havethe meaning of formula 1.

Examples of compounds which are suitable for the alkylation of8-hydroxyquinoline, in accordance with the invention, are the followingtypes of phenol obtainable according to DT-AS (German PublishedSpecification) No. 1,235,894 and aniline types obtainable according toDT-AS (German Published Specification) No. 1,191,363 or according toDT-OS (German Published Specification) No. 2,064,305:4-isopropenylphenol, 2-methyl-4-isopropenylphenol,2,6-dimethyl-4-isopropenylphenol, 2-propyl-4-isopropenylphenol,2-phenyl-4-isopropenylphenol, 2-chloro-4-isopropenylphenol,3-methyl-4-isopropenylphenol, 2-(p-hydroxyphenyl)-2-butene,2-(p-hydroxyphenyl)-2-pentene, 4-cyclohexenylphenol,2-(p-hydroxyphenyl)-2-(p-isopropenylphenyl)-propane,p-isopropenylaniline and p-isopropenylanilines which are substituted inthe phenyl nucleus by aryl, for example phenyl, alkyl, for example C₁-C₄ -alkyl, or halogen, for example chlorine or bromine.

Instead of the monomeric alkenylphenols and alkenylanilines it isequally well possible to use the dimers of these compounds, since thesere-dissociate to the monomers under the chosen reaction conditions.Dimeric isopropenylphenol of the following formula ##STR24## may bementioned as an example.

Other compounds which are suitable, in the present context, foralkylating 8-hydroxyquinoline and are able to form carbonium ions underthe influence of acid catalysts are, for example: 4-hydroxy-benzylalcohol, 2-bromo-4-hydroxybenzyl alcohol, 3,5-dibromo-4-hydroxy-benzylalcohol, 4-hydroxy-3,5-dimethyl-benzyl alcohol,4-hydroxy-2,6-dimethylbenzyl alcohol,4-hydroxy-2-isopropyl-5-methyl-benzyl alcohol, 2-phenyl-benzyl alcohol,3-phenyl-benzyl alcohol, 2-[4-hydroxyphenyl]-propanol,1-[4-hydroxyphenyl]-ethanol, 2-[4-hydroxyphenyl]-ethanol,2-[4-hydroxyphenyl]-2-[4-(1-hydroxypropyl-(2))phenyl]-propane,4-amino-benzyl alcohol and 2-chloro-4-aminobenzyl alcohol.

The reaction mixture is worked up as follows: the catalyst is firstremoved, if necessary after neutralisation, and solvent which may bepresent, and 8-hydroxyquinoline, are then removed in accordance withknown methods, for example by extraction, fractional crystallisation,vacuum distillation and steam distillation. Crystallisation of theresidue which remains, from suitable solvents such as, for example,benzene, toluene, ethanol, diethyl ether, acetone or mixtures of thesesolvents, gives the desired functional 8-hydroxyquinoles in good yields.They can be used direct for further reactions.

The following Examples A, B and C show the preparation of the compoundsof formula 1:

EXAMPLE A 2-[4-Hydroxyphenyl]-2-[5-(8-hydroxyquinolyl)]-propane

1508 g of 8-hydroxyquinoline, 483 g of p-isopropenylphenol and 150 g ofbentonite (acid catalyst K 20 from Messrs. Sudchemie, Munich) arebrought together and heated for 24 hours to 180° C. under reflux andunder a nitrogen atmosphere. The reaction mixture is then filteredthrough a pressure filter in order to remove the solid catalyst.

After addition of methylene chloride/water, a part of the2-[4-hydroxyphenyl]-2-[5-(8-hydroxyquinolyl)]-propane is obtained ascrystals. The mixture which remains is subjected to a steamdistillation, during which the 8-hydroxyquinoline employed in excess canbe recovered. On renewed addition of methylene chloride, a furtherproportion of the functional hydroxyquinoline is obtained as crystals.

The two crystalline fractions when combined give a total yield of 460 g(46% of theory). After extraction in a Soxhlet extractor with benzene,colourless crystals, of melting point 139° C., are obtained frombenzene.

    ______________________________________                                        Analysis:     C         H         N                                           ______________________________________                                        Calculated    77.4%     6.10%     5.01%                                       Found         77.5%     6.03%     4.87%                                       ______________________________________                                    

EXAMPLE B 2-[4-Aminophenyl]-2-[5-(8-hydroxyquinolyl)]-propane

2180 g of 8-hydroxyquinoline, 400 g of β-isopropenylaniline and 300 g ofbentonite (acid catalyst K 20 of Messrs. Sudchemie, Munich) are heatedto 160° C. for 26 hours under reflux and under a nitrogen atmosphere.The reaction mixture is filtered through a pressure filter and is thensuccessively subjected first to a vacuum distillation and then to asteam distillation. In the course thereof, the 8-hydroxyquinolineemployed in excess is recovered almost quantitatively. Methylenechloride is then added to the reaction mixture and the organic phase isseparated off. The residue which remains after concentrating the organicphase is extracted with a methylene chloride/petroleum ether mixture and382 g (46% of theory) of2-[4-aminophenyl]-2-[5-(8-hydroxyquinolyl)]-propane of melting point105°-107° C. are obtained. The melting point of the colourless crystalsrises to 109° C. on recrystallisation from ethanol.

    ______________________________________                                        Analysis:     C         H         N                                           ______________________________________                                        Calculated    77.7%     6.46%     10.02%                                      Found         77.5%     6.58%      9.88%                                      ______________________________________                                    

EXAMPLE C[4-Hydroxy-3,5-dimethyl-phenyl]-[5-(8-hydroxyquinolyl)]-methane

36.2 g of 8-hydroxyquinoline are solved in 200 ml acetic acid and at theboiling point of this solution within one hour a solution of 7.6 g of2.6-dimethyl-4-hydroxy-methylene-phenol in 50 ml acetic acid is addeddropwise. The mixture is boiled for 5 hours under reflux, thereafteracetic acid is withdrawn by vacuum-distillation and aceotropicdistillation. The non-reacted 8-hydroxyquinoline is removed by waterdistillation. The remaining compound is solved in CH₂ Cl₂ and filtered.By evaporation of the CH₂ Cl₂ 7.1 g of colourless crystals are obtained.Yield 47% of the theoretical amount.

    ______________________________________                                        Analysis:     C         H         N                                           ______________________________________                                        Calculated    77.5%     6.10%     5.01%                                       Found         77.2%     6.22%     5.04%                                       ______________________________________                                    

The examples which follow describe the preparation of somepolycondensates, containing 8-hydroxyquinoline end groups, of theformula 10, and of some polymers containing metal, of the formula 11 andthe use of the polycondensates of formula 10.

EXAMPLE 1

456 g of bisphenol A and 559 g of2-[4-hydroxyphenyl]-2-[5-(8-hydroxyquinolyl)]-propane are dissolved in 4kg of 9% strength sodium hydroxide solution and 9 kg of methylenechloride are then added. 562.8 g of phosgene are introduced withvigorous stirring and 60 ml of a 4% strength triethylamine solution arethen added dropwise. The mixture is stirred for a further hour and ifnecessary sufficient sodium hydroxide solution is added for the pH ofthe solution to remain constant at 13. The phases are separated and theaqueous phase is tested for complete conversion. The organic phase isextracted once with 5% strength H₃ PO₄, washed with water until neutraland subsequently dried over sodium-sulphate. The organic phase isconcentrated and the short-chain polycarbonate with hydroxyquinoline endgroups is obtained direct by precipitation in methanol. η_(rel) : 1.038(η_(rel) is measured in CH₂ Cl₂ at 20° C.; 0.5 g solved in 100 gsolution); nitrogen analysis: N₂ 2.56%; phenolic OH: 2.8%. The molecularweight calculated from these values is M_(n) =1178.

EXAMPLE 2

456 g of bisphenol A and 7 g of2-[4-hydroxyphenyl]-2-[5-hydroxyquinolyl)]-propane are dissolved in2.675 kg of 9% strength sodium hydroxide solution. 6 kg of methylenechloride are then added and 280 g of phosgene are introduced withvigorous stirring. Thereafter, 30 ml of a 4% strength triethylaminesolution are also added and the mixture is stirred for a further hour,during which the pH of the solution is kept at 13 by addition of sodiumhydroxide solution. Working up takes place as in Example 1. η_(rel) :1.517 (η_(rel) measured according to Example 1). M_(n) =178000(determined by membrane osmometry in dioxane).

EXAMPLE 3

114 g of bisphenol A, 9.30 g of2-[4-hydroxyphenyl]-2-[5-(8-hydroxyquinolyl)]-propane and 40 g of sodiumhydroxide are dissolved in 3 l of water. Thereafter, 300 ml of a 10%strength sodium lauryl-sulphate solution are also added. The reactionsolution is stirred vigorously and 101.6 g of isophthalic aciddichloride in 3 l of methylene chloride are then also added. Theresulting emulsion is stirred for a further 5 minutes and the product isthen precipitated in acetone. The polymer, containing hydroxyquinolineend groups, which is formed is filtered off and washed with water andacetone. The polyester purified in this way is dried in vacuo. η_(rel) :1.035 (η_(rel) measured according to Example 1). M_(n) =5500 (determinedosmometrically in dioxane).

EXAMPLE 4

7.65 g (7 mmols) of the polycarbonate with hydroxyquinoline end groups(M_(n) =1096) described in Example 1 are dissolved in 150 ml of absoluteCH₂ Cl₂ and a solution of 3.4 g of titanium tetra-butylate in 100 ml ofabsolute CH₂ Cl₂ is added progressively in 10 ml portions, the relativeviscosity being determined, as a measure of the growth of the molecularweight, after the addition of each 10 ml of the titanium tetra-butylatesolution. Table I below shows the relationship between the risingviscosity and the particular amount of metal compound added.

                                      TABLE I                                     __________________________________________________________________________                            Ratio of equivalents                                                          of polycondensate/                                    Material taken                                                                              Addition  metal compound                                                                          η.sub.rel                               __________________________________________________________________________    7.65 g of polycarbonate with                                                                10 ml of solution I.sup.x                                                               7:1       1.055                                       hydroxyquinoline end groups                                                   (M.sub.n = 1096)                                                              "             20 ml of solution I.sup.x                                                               7:2       1.066                                       "             30 ml of solution I.sup.x                                                               7:3       1.082                                       "             40 ml of solution I.sup.x                                                               7:4       1.093                                       "             50 ml of solution I.sup.x                                                               7:5       1.142                                       .sup.x Solution I: 3.4 g of titanium tetra-butylate in 100 ml of CH.sub.2     Cl.sub.2                                                                      Standard according to Example 1   1.038                                       __________________________________________________________________________

EXAMPLE 5

1.78 g of the polycarbonate, containing hydroxyquinoline end groups(M_(n) =17800), prepared in Example 2 are dissolved in 100 ml ofabsolute CH₂ Cl₂ and 10 ml of this solution are taken. To this is addeda solution of 3.83 g of zirconium tetra-butylate in 1 l of absolute CH₂Cl₂ in 1 ml portions introduced dropwise, and after each addition therelative viscosity is determined, as in Example 4.

                                      TABLE 2                                     __________________________________________________________________________                            Ratio of equivalents                                                          of polycondensate/                                    Material taken          metal compound                                                                          η.sub.rel                               __________________________________________________________________________    1.78 g of polycarbonate with                                                                1 ml of solution II.sup.(x)                                                             10:1      1.714                                       hydroxyquinoline end groups                                                   (Mn = 17800)                                                                  "             2 ml of solution II.sup.(x)                                                             10:2      1.844                                       "             3 ml of solution II.sup.(x)                                                             10:3      2.083                                       "             4 ml of solution II.sup.(x)                                                             10:4      2.419                                       "             5 ml of solution II.sup.(x)                                                             10:5      2.635                                       "             6 ml of solution II.sup.(x)                                                             10:6      2.705                                       .sup.(x) Solution II: 3.83 g of zirconium tetra-butylate in 1 l of            CH.sub.2 Cl.sub.2                                                             Standard according to Example 2   1.517                                       __________________________________________________________________________

EXAMPLE 6

5 g of the polycarbonate (M_(n) =17800) prepared in Example 2 aredissolved in 180 ml of absolute CH₂ Cl₂ and 14 ml, 21 ml and 28 ml of asolution of 0.383 g of zirconium tetrabutylate in 100 ml of absolute CH₂Cl₂ are added dropwise. The resulting chain-lengthened polycarbonatescontaining zirconium were isolated and converted to films. Table 3 showsthe yield stress δ_(S), the tensile strength δ_(R), the elongation atbreak ε_(R) and the modulus of elasticity of the films and relates theseto the metal content of the particular polycondensate.

                  TABLE 3                                                         ______________________________________                                        Ratio of equivalents of                                                       polycondensate/                                                                             δS δR εR                                                                         E-modulus                                metal compound                                                                              (kp/cm.sup.2)                                                                          (kp/cm.sup.2)                                                                          %    (kp/cm.sup.2)                            ______________________________________                                        1:0,5         533      509      69.3 27000                                    1:0,75        500      500      50.6 28400                                    1:1           516      500      50.8 29700                                    ______________________________________                                    

The yield stress, the tensile strength and the elongation at break aremeasured according DIN 53 455; the ε-modulus is measured according DIN53 457.

EXAMPLE 7

24 g of a polycarbonate prepared according to Example 2, with8-hydroxyquinoline end groups and a molecular weight M_(n) =11980(measured by membrane osmometry in dioxane) are dissolved in 200 ml ofabsolute CH₂ Cl₂ and 0.476 g of titanium tetrabutylate in absolute CH₂Cl₂ is added.

The polycondensate containing metal was converted to a film and themodulus of elasticity (according DIN 53 457) and glass transitiontemperature thereof were determined. In addition, the molecular weightwas determined osmometrically.

                  TABLE 4                                                         ______________________________________                                                     M.sub.n determined                                                            osmometrically                                                                             Glas                                                Ratio of equivalents                                                                       M.sub.n of starting                                                                        transition                                          of polycondensate/                                                                         substance =  tempera- E-modulus                                  metal compound                                                                             11980        ture (°C.)                                                                      (kp/cm.sup.2)                              ______________________________________                                        2:1.4        M.sub.n 18800                                                                              154.5    22700                                      ______________________________________                                    

EXAMPLE 8

8 g of a polycarbonate of M_(n) =16000 (measured by membrane osmometryin dioxane), prepared according to Example 2, were dissolved in 100 mlof absolute CH₂ Cl₂ and a solution of 0.32 g of titanium tetra-butylatepolymer in 20 ml of CH₂ Cl₂ was added. The resulting polycarbonatecontaining titanium was examined by differential thermo-analysis. Table5 shows the glass transition temperature which has been raised byincorporation of the metal.

                  TABLE 5                                                         ______________________________________                                                    Glass trans-                                                                  ition temperat-                                                               ture        Glass trans-                                                      Polycondensate                                                                            ition tempera-                                                                           Heat                                       Ratio of equivalents                                                                      with hydroxy-                                                                             ture       stability                                  of polycondensate                                                                         quinoline end                                                                             Metal poly-                                                                              according                                  metal compound                                                                            groups      condensate DIN 53735                                  ______________________________________                                        1:0.5       145° C.                                                                            162° C.                                                                           decomposi-                                                                    tion above                                                                    350° C.                             ______________________________________                                    

EXAMPLE 9

1.78 g portions of the polycarbonate with 8-hydroxyquinoline end groups,prepared in Example 2, are reacted with the metal acetylacetonateslisted in Table 6, in the molar ratio of 1:1, by heating to 140° C. indichlorobenzene for two hours.

                                      TABLE 6                                     __________________________________________________________________________                                              Metal content                                                                 (% by weight)                       Material taken             Addition       calculated                                                                          found                         __________________________________________________________________________    1.78 g of hydroxyquinoline-polycarbonate (M.sub.n = 17800                                                26 mg of cobalt acetylacetonate                                                              0.33  0.33                          "                          27 mg of nickel acetylacetonate                                                              0.33  0.34                          "                          35 mg of iron acetylacetonate                                                                0.32  0.31                          It proved possible to convert all the polycarbonates containing metal to      films. The film                                                               containing cobalt was tested according DIN 53 455                             __________________________________________________________________________

It proved possible to convert all the polycarbonates containing metal tofilms. The film containing cobalt was tested tensometrically: accordingDIN 53 455

    ______________________________________                                        Tensile strength     δ.sub.R (kp/cm.sup.2):585                          Elongation at break  ε.sub.R %:51                                     E-modulus (DIN 53 457)                                                                             (kp/cm.sup.2):28500                                      ______________________________________                                    

EXAMPLE 10

3 g portions of the polyester with 8-hydroxyquinoline end groups (M_(n)=5500), described in Example 3, are dissolved in 100 ml of absolute CH₂Cl₂ and the following metal alcoholate solutions are added in equivalentamounts:

1. 10 ml of a solution of 1.77 g of titanium tetra-butylate in 100 ml ofabsolute CH₂ Cl₂,

2. 10 ml of a solution of 2 g of zirconium tetra-butylate in 100 ml ofabsolute CH₂ Cl₂.

                  TABLE 7                                                         ______________________________________                                                                   Metal content                                                                 (% by weight)                                      Material taken Addition    calculated                                                                              found                                    ______________________________________                                        3 g of polyester with                                                                        0.177 g of  0.83%     0.75%                                    8-hydroxyquinoline end                                                                       Ti(C.sub.4 H.sub.9 O).sub.4                                    groups (M.sub.n 5500)                                                         3 g of polyester with                                                                        0.200 g of  1.6%      1.4%                                     8-hydroxyquinoline end                                                                       Zr(C.sub.4 H.sub.9 0).sub.4                                    groups (M.sub.n 5500)                                                         ______________________________________                                    

EXAMPLE 11 Polyester from aliphatic dicarboxylic acids.

A mixture of 7,87 g of adipic acid dichloride, 4,28 g of hydroquinoneand 1.32 g of 2-[4-hydroxyphenyl]-2[5-(8-hydroxyquinolyl)]-propane and20 ml of nitrobenzene are slowly in a heated dry atmosphere within 2.5hours up to 150° C. and is kept at this temperature for a further 6hours. During the total reaction an N₂ -stream is passed through thereaction mixture. The nitrobenzene is distilled off under reducedpressure and the solid residue is dried. The polycondensate obtained hasa molecular weight Mn of 7600 determined by membrane osmometry indioxane.

EXAMPLE 12 Polyamide

A mixture of 55 g of N,N'-diethyl-ethylenediamine and 6.95 g of2-(4-aminophenyl)-2-[5-(8-hydroxyquinolyl)]-propane and 106 g of Na₂ CO₃in 2.5 l of H₂ O is throughly mixed. A solution of 101 g of terephthalicacid dichloride in 800 ml of dry CHCl₃ is added within 10 minutes. TheCHCl₃ is distilled off from the reaction mixture; the polycondensateobtained is filtered off, washed with water four times: 98 g of a driedpolycondensate is obtained having a η_(rel) of 1.95 (η_(rel) isdetermined in cresol at 25° C., 1% by weight solution).

EXAMPLE 13

Use of the polycarbonate of Example 1 as absorbing agent. 5 g of thepolycarbonate of Example 1 are dissolved in 100 ml of CH₂ Cl₂ andagitated with a solution of 2 g of ##STR25## in 100 ml of H₂ O for 2hours at 20° C. Thereafter the phases are separated and the organicphase is dried. The resulting polymer contains 0.99 of Hg whichcorresponds to a content of 19.8% by weight. This shows the goodcapacity of the polycondensates of formula 10 for absorbing heavy metalions.

EXAMPLE 14

Use of the polyamide of Example 12 as absorbing agent. According toExample 13 5 g of the polyamide of Example 12 are dissolved inchloroform and agitated together with a solution of 8.15 g of ##STR26##in 100 ml of H₂ O for two hours at 20° C. The H₂ O-phase is separatedand the CHCl₃ is distilled off: The remaining polymer has an Hg-contentof 5.1% by weight. This shows the good capacity of the polycondensatesof formula 10 for absorbing heavy metal ions.

The Hg-containing polymer has the structure of the products of formula11 and is therefore an example for producing a metal-containingpolyamide of formula 11.

What we claim is:
 1. Polycondensates of the formula ##STR27## wherein R¹and R² are identical or different and denote hydrogen, (C₁ -C₄)-alkyl,phenyl or halogen and Z is CH₂, CH--CH₃, an isoalkylidene radical with 3to 5 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to15 carbon atoms, or a radical of the formula ##STR28## in which R⁴, R⁵and R³ are identical or different alkyl radicals with 1 to 5 carbonatoms, andwherein M is a polycarbonate segment of the formula ##STR29##wherein D is chlorine, bromine, hydrogen or C₁ -C₄ alkyl, L is a singlebond, C₁ -C₅ alkylene, C₂ -C₅ -alkylidene, C₅ -C₁₅ cycloalkylene, C₅-C₁₅ cycloalkylidene or a radical of the formula ##STR30## and p is aninteger between 2 and
 50. 2. Polymers of the formula ##STR31## wherein Qis either a group of the formula ##STR32## or T and whereinR₁, R₂, Z andM are as defined in claim 1 n is between 1 and 50 and G corresponds tometal compounds of the formula ##STR33## in which m is the number ofanion bonds or ligands Ton the metal atom and is calculated from thedifference of the valency or co-ordination number minus two, r is aninteger from 0 to 20, Me is a metal of sub-group 1 to 8 or of main group2 to 5 and T corresponds to anions of inorganic mineral acids, anions oforganic carboxylic acids, complex-forming agents, C₁ -C₁₈ -alkoxyradicals, C₆ -C₁₂ -aryloxy radicals or trialkylsiloxy radicals with 3 to12 carbon atoms and E is H or ##STR34##
 3. The polycondensates of claim1 wherein M₁ has a molecular weight determined by membrane osmometry at20° C. of from 1,000 to 30,000.
 4. The polycondensates of claim 1wherein M₁ is based on a bisphenol which is 4,4'-dihydroxydiphenyl;bis-(4-hydroxyphenyl)-propane-2,2;bis-(4-hydroxy-3,5-dichlorophenyl)-propane-2,2;bis-(4-hydroxy-3,5-dibromophenyl)-propane-2,2;bis-(4-hydroxy-3,5-dimethylphenyl)-propane-2,2;bis-(4-hydroxy-3-methylphenyl)-propane-2,2 orbis-(4-hydroxyphenyl)-cyclohexane-1,1.
 5. The polycondensates of claim 1wherein R¹ and R² are chlorine or bromine.
 6. The polycondensates ofclaim 1 wherein Z is selected from the group consisting of ##STR35## 7.The polycondensates of claim 1 wherein Z is ##STR36## and R¹ and R² arehydrogen.
 8. The polycondensates of claim 1 wherein Z is ##STR37## R¹and R² are each hydrogen and M₁ is based onbis(4-hydroxyphenyl)-propane-2,2.
 9. The polymers of claim 2 wherein M₁has a molecular weight determined by membrane osmometry at 20° C. offrom 1,000 to 30,000.
 10. The polymers of claim 2 wherein M₁ is based ona bisphenol which is 4,4'-dihydroxydiphenyl;bis-(4-hydroxyphenyl)-propane-2,2;bis-(4-hydroxy-3,5-dichlorophenyl)-propane-2,2;bis-(4-hydroxy-3,5-dibromophenyl)-propane-2,2;bis-(4-hydroxy-3,5-dimethylphenyl)-propane-2,2;bis-(4-hydroxy-3-methylphenyl)-propane-2,2 orbis-(4-hydroxyphenyl)-cyclohexane-1,1.
 11. The polymers of claim 2wherein R¹ and R² are chlorine or bromine.
 12. The polymers of claim 2wherein Z is selected from the group consisting of ##STR38##
 13. Thepolymers of claim 2 wherein Z is ##STR39## and R¹ and R² are hydrogen.14. The polymers of claim 2 wherein Z is ##STR40## R¹ and R² are eachhydrogen and M₁ is based on bis-(4-hydroxyphenyl)-propane-2,2.
 15. Thepolymers of claim 2 wherein Me is selected from the group consisting ofSc to Zn, Y to Cd, La to Hg, Ac to U, Al, Pb and Bi.
 16. The polymers ofclaim 2 wherein T is the anion of an inorganic acid selected from thegroup consisting of HCl, H₂ SO₄, H₃ PO₄ and HNO₃.
 17. The polymers ofclaim 2 wherein T is the anion of a saturated aliphatic carboxylic acidhaving 1 to 18 carbon atoms.
 18. The polymers of claim 2 wherein Tcorresponds to the anion of a member selected from the group consistingof HCOOH, (COOH)₂, CH₃ COOH and CH₃ (CH₂)₁₆ COOH.
 19. The polymers ofclaim 2 wherein T is a complex forming agent selected from the groupconsisting of aliphatic diketones, ethylenediaminetetracetic acid,nitrilotriacetic acid and cyclopentadiene.